Imperial College London
Alternate

Professor Mike Robb, FRS

Faculty of Natural Sciences, Department of Chemistry

Chair in Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 5757mike.robb Website

 
 
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Location

 

301cMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Polyak:2018:10.1080/00268976.2018.1478136,
author = {Polyak, I and Jenkins, A and Vacher, M and Bouduban, M and Bearpark, M and Robb, MA},
doi = {10.1080/00268976.2018.1478136},
journal = {Molecular Physics},
pages = {2474--2489},
title = {Charge migration engineered by localisation: electron-nuclear dynamics in polyenes and glycine},
url = {http://dx.doi.org/10.1080/00268976.2018.1478136},
volume = {116},
year = {2018}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - We demonstrate that charge migration can be ‘engineered’ in arbitrary molecular systems if a single localised orbital – that diabatically follows nuclear displacements – is ionised. Specifically, we describe the use of natural bonding orbitals in Complete Active Space Configuration Interaction (CASCI) calculations to form cationic states with localised charge, providing consistently well-defined initial conditions across a zero point energy vibrational ensemble of molecular geometries. In Ehrenfest dynamics simulations following localised ionisation of -electrons in model polyenes (hexatriene and decapentaene) and -electrons in glycine, oscillatory charge migration can be observed for several femtoseconds before dephasing. Including nuclear motion leads to slower dephasing compared to fixed-geometry electron-only dynamics results. For future work, we discuss the possibility of designing laser pulses that would lead to charge migration that is experimentally observable, based on the proposed diabatic orbital approach.
AU  - Polyak,I
AU  - Jenkins,A
AU  - Vacher,M
AU  - Bouduban,M
AU  - Bearpark,M
AU  - Robb,MA
DO  - 10.1080/00268976.2018.1478136
EP  - 2489
PY  - 2018///
SN  - 0026-8976
SP  - 2474
TI  - Charge migration engineered by localisation: electron-nuclear dynamics in polyenes and glycine
T2  - Molecular Physics
UR  - http://dx.doi.org/10.1080/00268976.2018.1478136
UR  - http://hdl.handle.net/10044/1/59830
VL  - 116
ER  -
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